Azo-dyestuffs and process of making same



Patented July 14, 1936 UETED STATE rrest orricE AZO-DYESTUFFS AND rnoonss OF MAKING SAME No Drawing. Application November 17, 1931, Serial No. 575,681. In Switzerland December 23 Claims.

The present invention relates to the manufacture of new azo-dyestuffs which are useful for the most various purposes, particularly for the production of fast tints on vegetable and animal fibers. They may also be used for coloring varnishes, as acetate silk dyestuffs, or, in case they contain suitable groups, such as, for example, sulfonic groups, as Wool dyestuffs dyeing in an acid bath. The invention comprises the process of making these dyestufis, as well as the new dyestuffs themselves.

All these dyestuffs are obtained by combining any diazo-compounds with arylides, made by con densing primary aromatic amines containing up to two amino-groups with hydroxy-carboxylic acids of the benzene series, which are so substituted that they can couple with diazo-compounds in ortho-position to the OH-group. Among the dyestuffs obtained, those are particularly valuable which are made from unsulfonated diazo-compounds, and among these particularly those are again of importance for the production of fast tints on cotton, which are made by combining unsulfonated or uncarboxylated diazo-compounds with the diarylides of the general formula OHI [HO X X wherein the two Xs stand for hydrogen, alkyl or alkoxy, and the two Rs stand for the benzene nucleus of the said acid.

For the production of fast tints on animal fibers, for example wool or silk, not only the above cited arylides are suitable, but also those which derive from other diam'ines, such as, for example, from p-phenylenediamine, m-phenylenediamine, naphthalenediamines, such as 1,5-naphthalenediamine, m,mazoxyaniline, 3,3-diaminomonobenzoyl-m-phenylenediamine, p,p'-diaminoazo benzene, diam'inoanthraquinones, diaminodiarylether, 3,3- or 2,2'-dichlorbenzidine, 4,l'-diaminostilbene, 4,4-diaminodiphenylurea, diaminocarbazols, diaminoacridines, diaminodiphenylmethanes, diaminotriphenylmethanes, diaminoacridones, etc., or also from simple amines, such as aniline, the toluidines, the xylidines, or also from polynuclear monoamines, such as naphthylamines, aminonaphthols and the sulfonic acids thereof, dehydrothiotoluidine and the sulfonic acid thereof, aminobenzimidazols, aminoquinolines, etc. The new dyestuffs may also be produced on other materials, such as, for example, on artificial silks from regenerated cellulose, or

(ill. 260--76) on acetylated cellulose. They may also be produced without substrata, or on precipitated substrata, and may therefore be used in the form of lacquers or pigments. Finally, as already mentioned, also acid dyestuffs may be obtained if 5 sulfonated diazo-compounds are used.

As hydroxycarboxylic acids of the benzene series which couple in ortho-position to the OH- group, p-cresotinic acid may above all be mentioned. Also other acids come into consideration, such as, for example, p-hydroxybenzoic acid, 3- methyl-l-hydroxy-l-benzoic acid, ,B-resorcylic acid, c-resorcylic acid--monomethylether, monobrominated fi-resorcylic acid, etc.

With the new dyestuffs deep brown to reddish brown, yellow-brown, brown-orange }to yellow tints are quite generally obtained, which may be distinguished by quite remarkable properties of fastness. They all correspond to the general formula 20 Example 1 21.8 parts of para-nitraniline-sulfonic acid are diazotize'd as usual and the diazo-solution is introduced into one of 22.8 parts of para-'cresotinic acid-anilide, 30 parts of caustic soda solution of 30 per cent. strength, 15 parts of soda ash and 200 parts of water. The dyestuff produced is precipitated rather quickly, and. what remains may be salted out. The brown precipitate is filtered and dried. The dyestuff which corresponds Very probably with the formula I O H dyes wool in an acid bath brown tints, which become darker when after-chromed.

Example 2 formula O H l is filtered, washed and dried.

Example 3 One part of cotton yarn is impregnated at 20-25" C. for hour in 20 parts of a liquor containing per litre 6 grams of di-(para-cresotinic acid) -dianisidide, 10 cc. of caustic soda solution of 34 B., 7 cc. of Turkey red oil, 6 cc. of formaldehyde solution of 40 per cent. strength and 10 grams of common salt; the yarn is then well wound off and developed in a solution, neutralized with sodium bicarbonate and containing per litre 10 grams of a diam-preparation of 20 per cent. strength made from -chloro-Z-aminodiphenyl-ether and 1,3,6-naphthalene-trisulfonic acid. The yarn is then rinsed and soaped. There is produced a very pure brown tint of good properties of fastness. The formula of the new dyestufi corresponds very probably with the formula I 1 OH H tim r 1 O H l H CN CH3 CH3 II I I C] CH3 Example 4 The material to be printed is padded with an alkaline solution containing per litre 10 grams of di-(para-cresotinic acid) -to1idide. After drying, it is printed with a printing color which contains per kilo 8 grams of diazotized 1-amino-2,5- dichloro-e-benzoylaminobenzene. The pure yellow-brown dyeing develops quickly and is very fast. The formula of the new dyestuff corresponds very probably with the formula on o lT I H O o I H CH3 Cl Fast prints may also be obtained in an advantageous manner with aid of preparations which have been made in known manner from the alkali salts of the respective arylides and suitable nitrosamines or diazo-amino compounds.

Example 5 0.6 parts of di-(p-cresotinic acid) -benzidide are boiled for a short time with 5 parts by volume of alcohol, 9 parts by volume of Turkey red oil 1:1, and 3 parts by volume of caustic soda solution of 36 B., and then introduced into a solution of 36 parts by volume of sulfite cellulose waste liquor of per cent. strength, 18 parts of common salt in 900 parts of water. In this grounding bath 30 grams of a wool skein are treated for hour at 45 C., the material being frequently moved about. The wool is then well Washed, slightly centrifuged, and introduced into a developing bath containing 4.5 grams of diazotized i-nitro-o-phenetidine per litre, and neutralized with sodium bicarbonate. The wool skein is allowed to remain in the developing bath for 20 minutes, whereupon it is Withdrawn, well rinsed and then acidified for 20 minutes at 80 C. in a bath containing 1.2 grams of sulfuric acid in the litre (corresponding to 4 per cent. sulfuric acid calculated on the weight of the wool) There is thus obtained a dark brown tint of good properties of fastness.

In the following table are set forth some of the tints which can be produced on the fiber by this invention:

O OH OH O I l l H HQQH O H l H 0 i a I CH3 CH3 I C1 CH3 CH3 Cl Diazo-component Coupling component Tint on cotton 1 2,5-dicl1lorani1ine Di-(para-cresotonic acid)-dianisidide Brown 2 l-amino-Q-nitro-4-rnethyl-5-be11z0y1-aminobenzcno do Reddish dark brown 3 4-cl1loro-ortho-anisidine do Khaki brown 4 l-uitro-orthonnisidine do Maroon brown 5 Meta-nitro-para-toluidinc "do. Reddish dark brown 6 4-cl1loro-11itraniline do Heddish maroon 7 anitro-ortho-anisidina .do, Grey brown 8 Meta-nitrdpara-phenetiiiine "do Yellowish brown 9 Meta-nitro-para-anisi dine ido Do. 10 l-amino-Z-nitro-4-mcthoxy-5-beuzoyl-aminobenzene d Olive The formula, of dyestuif No. 1 is very probably I CH3 Diem-component Coupling component Tint on cotton 11 4-ch101'0-4-am1'n0-3-nitrodiphenyl-ether Brown 12 l-arnino-2-ohloro-fi-metzhoxybenzene Yellowish brown 13 4-nitro-ortho-phenetidrne Reddish brown 14 4,5-dioh1oro-Z-aminodiphenylether Brown 15 S-nitro-ortho-phenetidine Reddish brown 16 Ortho-nifm'niline D 17 -nitro-ortho-toluidine 4. Do. 18 4-cl110r0-2-amin0-4-methyldiphenyl-ether Yellow brown 19 4-aminobenzene-l-azodiphenylamine Bordeaux brown 20 1-amino-2,5-diohloro-4-benzoylaminobenzene Yellow brown 21 l-amino-2-methoxy-5ohloro-4-benzoylaminobenzene. Khaki-brown 22 4-amino-4-ethoxydiphenylamine Roddish brown 23 Dianisidine Maroon 24 Ortho-ohloraniline Brown 25 Meta-nitro-orthotoluidine Reddish-brown 26 Para-nitraniline Brown 27 4-aminoazobenzene. Do. 28 4-amino-5-methoxyazobenzene Reddish brown 29 4-ch]or0-4-a1nino-5-methoxyazobenzene Maroon 30 4-ohloro-2-aminodiphenylother Brown 31 4-ol1loro-2-amino-4-n1ethyldipheny1-ether Do. 32 4,4dichloro-2-aminodiphenylether Do. 33 4aminobenzene-l-azodiphenylamine Red-brown 34 1-amino-2,5-diehloro-4-benzoylaminobenzene.. Yellow-brown 35 Para-nitraniline. Brown 36 Ortho-nitran1l1ne Reddish-brown 37 5-nitr0-orthotoluid1ne Do. 38 Dianisidine- Maroon 39 Nitro-metaxy1 Yellowish brown 40 2,5-diohlor-aniline Brown 41 l-amino-2-nitro-4-methyl-5-benzoyl-aminobenzene Red brown 42 4-chloro-4-amino-3-nitrodiphenyl-ether Reddish brown 43 4-nitro-0rth0-phenetidine Brown 44 4,5-diohloro-2-aminodiphenylether Do. 45 5nitro-ortho-phenetidine. Dark brown 46 4-nitro-ortho-anisidine. Brown 47 Meta-nitro-para-toluidin Reddish dark brown 48 4-chloro-2-nitraniline Brown 49 4-eh1or0-2-arnino-4-methy1diphenyl-ether. Do. 50 4,'4-dichloro-Z-aminodiphenylether Do. 51 l-amino-Z,5-diohloro-4-benzoylamino-benzene Yellowish brown 52 4-nitro-ortho-toluidine Reddish brown 58 2,5-dich1oraniline n. Brown 54 l-emino-Z-nitro-4-metl1yl-5-benzoyl-aminobenzene Dark brown 55 4,s-dichloro-zaminodiphenylether Reddish brown 56 5-nitro-ortho-toluidine Brown 57 4-ohloro-4-amino-3-nitro-diphenylether Reddish brown 58 4-nitro-ortho-anisidine Brown 59 Meta-nitro-para-t0luidine Dark brown 6Q 4-chloro-2-nitraniline Do. 61' 4-chloro-2-amino-4-ohlorodiphenylether. Di-(para-oresotinic acid)-dianis1d1de Yellow brown 62 4 011loroQ-arninodiphenylether Di-(2,4-dihydr0xybenzoio acid)-dianisid Brown 63 5-ohloro-2-toluidine.. Di-(5-bromo-2, 4-dihydroxybenzoic aoid)-dionisidido Bright brown 64 2,5-dichloraniline do w 65 B-naphthylamine Di-(para-oresotinio 8Cid).-IIO]1 id Bright brown Tint on wool 66 Ortho-nitraniline Di-(para-cresotinlc acid)-paraphenylenediamido Brown- 67 2, 5-diol1loraniline. do Yellow brown 68 Ortho-nitranilinm, Di-(para-cresotinic aoid)-azoxyaniline-m,m-diamide Brown 69 lVIeta-nitro-p-toluidine n. Di-(para-cresotinio acid)-1,5-naphthylenediamide... Deep brown 70 Orthonitraniline Di-(para-hydroxybenzoio acid)-benzidide Yellow brown 71 Do o Di-(para-hydroxybenzoic aoid)-dianisidide 4. D 72 Do Di-(para-oresotinic acid)-3,3 -dich1or0benzidide Brown 73 Do r. Mixed diarylido from 1 molecular proportion of p- Reddish brown cresotinic acid and one molecular proportion of 2,3- hydroxyuaphthoio acid and dianisidine. 74 Do Mixed diarylide from 1 molecular proportion of para- Brown.

cresotinic acid and 1 molecular proportion of orthooresotinic acid and benzidine. 75 Do Arylide from para-cresotinic acid and 5-ol1lor-0rtho- Do. toluidide.

76 Do Arylide from para-cresotinic acid and 2,5,7-a1m'no- Do.

naphthol sulfonlc acid. 77 Do Arylide from para-cresotinie acid and dehydrothio- Do.

toluidine sulfonic acid. 78 Do Arylide from para-cresotinic acid and a-naphthyi- Do,

31111119. 79 4-nitro-ortho-nnisidine .do Yellow brown 80 4-eh10ro-2-to1uidine Aayiido from para-oresotinio acid and para-phene- Do.

1 ne. 81 2,5-dichloraniline Artyiidoa from para-cresotinio acid and dehydro-thio- Golden yellow o 111 me. 82 Meta-chloraniline do Do. 83 D Arylide from para-cresotinio acid and Reddish golden yelmethyl-benzimidazol. low

IMO M The formula of dyestuff N0. 62 is very probably N m a a CH0 w H m f The formula of dyestuff No. 66 is very probably The formula of dyestufi N0. 76 is very probably OH 1Y0; OH

N s N:N

The formula of dyestuif No. 81 is very probably The formula of dyestufi No. 70 is very probably arr- 3 O H -CH:

IIIO 2 45 N02 (|)H ONNO The formula of dyestuff No. 7 3 is very probably The formula of dyestuff No. '75 is very probably What we claim is:-

1. Process for the production of azo-dyestuffs consisting in coupling diazotized aromatic amino compounds with arylides made by condensing a hydroxycarboxylic acid of the following formula Y COOH wherein one X stands for OH, the Y in para position to the OH stands for alkyl or alkoxy, and the remaining X and Y stand for hydrogen, with a primary aromatic amine of the benzene, naphthalene or diphenyl series which may contain up to two amino groups.

2. Process for the production of azo-dyestuifs consisting in coupling diazotized aromatic amino compounds with arylides made by condensing para-cresotinic acid with a primary aromatic .amine of the benzene, naphthalene or diphenyl series which may contain up to two amino groups.

3. Process for the production of azo-dyestuffs consisting in coupling diazotized aromatic amino compounds with arylides made from one molecular proportion of an aromatic diamine of the benzene, naphthalene or diphenyl series and two molecular proportions of such aromatic hydroxycarboxylic acids as are capable of coupling with diazo compounds, of which at least one molecular 4 proportion consists of a hydroxycarboxylic acid of the following formula COOH wherein one X stands for OH, the Y in para position to the OH stands for alkyl or alkoxy, and the remaining X and Y stand for hydrogen.

4. Process for the production of azo-dyestuiis consisting in coupling diazo-tized aromatic amino compounds with arylides made from one molecular proportion of an aromatic diamine of the benzene, naphthalene or diphenyl series, one molecular proportion of para-cresotinic acid, and one molecular proportion of an aromatic hydroxycarboxylic acid which is capable of coupling with diazo compounds.

5. Process for the production of azodyestuifs which comprises coupling a diazotized aromatic amino compound with an arylide made by condensing one molecular proportion of an aromatic diamine of the benzene, naphthalene and diphenyl series with two molecular proportions of 2-hydroxy-5-methyl benzoic acid.

6. Process for the production of azo-dyestuffs comprising coupling unsulfonated diazotized aromatic amino compounds with arylides made from one molecular proportion of a diamine of the general formula wherein X stands for hydrogen, alkyl or alkoxy,

and two molecular proportions of a hydroxycarboxylic acid of the formula wherein one X stands for 01-1, the Y in para position to the OH stands for alkyl or alkoxy, and the remaining X and Y stand for hydrogen.

7. Process for the production of azodyestufis comprising coupling diazotized unsulfonated primary aromatic mono-amines with arylides of the general formula GOOH wherein one X stands for OH, the Y in para position to the OH stands for alkyl or alkoxy, and the remaining X and Y stand for hydrogen.

9. Process for the production of azo-dyestuffs, consisting in coupling diazotized unsulfonated oamino-diphenyl others which are halogenated in the nucleus containing amino-groups, with arylides of the general formula wherein X stands for hydrogen, alkyl or alkoxy.

10. Process for the production of an azo-dyestuff, consisting in coupling the diazotized 4- chloro-Z-amino-diphenyl ether with the diarylide from one molecular proportion of benzidine and two molecular proportions of p-cresotinic acid.

11. Process for the production of an azo-dyestufi, consisting in coupling the diazotized 4,4- dichloro-Z-amino-diphenyl ether with the diarylide from one molecular proportion of benzidine and two molecular proportions of p-cresotinic acid.

12. Process for the production of an azo-dyestuff, consisting in coupling the diazotized 4.- chloro-Z-amino-diphenyl ether with the diarylide from one molecular proportion of tolidine and two molecular proportions of p-cresotinic acid.

13. The azoclyestuff obtained by combining a diazotized aromatic amino compound and an arylamide of the following formula:

H3O CONHR wherein R is a benzene, naphthalene or a diphenyl nucleus.

14. The azo-dyestuifs which correspond to the general formula wherein R1 stands for the radical of a diazotized aromatic amino compound, R2 for a benzene nucleus containing an OH-group in ortho position to the -N:N group, and R3 an aromatic radical of the benzene, naphthalene or diphenyl series which may contain further azo groups, which dyestuffs are obtained by coupling diazotized aromatic amino compounds with arylides made by condensing hydroxy-carboxylic acids of the benzene series which are substituted by an alkyl or an alkoxy group in para position to the OI-I-group and which contain no other substituents, with primary aromatic amines of the benzene, naphthalene or diphenyl series which may contain up to two amino groups, and which dyestuffs in a dry state are yellow-brown to dark colored powders which dye the fiber fast yellow, orange, brown and dark brown tints.

15. The azo-dyestuifs which correspond to the general formula 1 OH HO wherein R4 stands for the radical of a diazotized aromatic amino compound, R2 for a benzene nucleus containing an OH-group in ortho position to the -N=N group, R1 for an aromatic radical, R3 for an aromatic nucleus containing at least one OH-group in ortho or para position to wherein R4 stands for the radical of a diazotized aromatic amino compound, R2 and R3 for a benzene nucleus containing an OH-group in ortho position to the -N=N group, R1 for an aromatic radical, which dyestuifs are obtained by coupling diazotized aromatic amino compounds with arylides made from one molecular proportion of an aromatic diamine of the benzene, naphthalene and diphenyl series and two molecular proportions of a hydroxycarboxylic acid of the benzene series which is substituted by an alkyl or an alkoxy group in para position to the OI-I-group and which contains no other substituents, and which dyestufis in a dry state are dark brown powders and, when produced on the fiber, dye the same brown tints which are intensive.

17. The azo-dyestuffs which correspond to the general formula 0 H 1 H o wherein R4 stands for the radical of an unsulfonated diazotized aromatic amino compound, R2 for a benzene nucleus containing an OI-I-group in ortho position to the N=N group, and X for hydrogen, alkyl or alkoxy, which dyestufis are obtained by coupling unsulfonated diazotized aromatic amino compounds with arylides made from one molecular proportion of a diamine of the general formula wherein X stands for hydrogen, alkyl or alkoxy, and two molecular proportions of a hydroxycarboxylic acid of the benzene series which is substituted by an alkyl or an alkoxy group in para position to the OH-group and which contains no other substituents, and which dyestuffs in a dry state are dark brown powders and, when produced on the fiber, dye the same brown tints which are intensive.

18. The azo-dyestuffs which correspond with the general formula the -N- N-- group, which dyestufis are obtained by coupling diazotized aromatic amino compounds with arylides made from one molecular proportion of an aromatic diamine of the benzene, naphthalene or diphenyl series and two molecular proportions of aromatic hydroxycarboxylic acids capable of coupling with diazo compounds, of which at least one molecular proportion consists of a hydroxy-carboxylic acid of the benzene series which is substituted by an alkyl or an alkoXy group in para position to the OH-group and which contain no other substituents, and which dyestuffs in a dry state are dark brown powders and, when produced on the fiber, dye the same brown tints which are intensive.

16. The azo-dyestuffs which correspond to the general formula wherein R4 stands for the radical of a diazotized unsulfonated primary aromatic mono-amine, and X for hydrogen, alkyl or alkoxy, which products are obtained by coupling diazotized primary aromatic monoamines with arylides of the general formula I CH:

19. The azo-dyestuffs which correspond to the general formula the nucleus containing amino-groups, and X for hydrogen, alkyl or alkoxy, which products are OHI IHO X X wherein X stands for hydrogen, alkyl or alkoxy and two molecular proportions of a hydroxycarboXylic acid of the benzene series, which is substituted by an alkyl or an alkoxy group in paraposition to the OH-group and which contains no other substituents, and which dyestuffs, in a dry state, are dark brown powders, and, when produced on the fiber, dye the same brown tints Which are intensive.

20. The azo-dyestufis which correspond to the obtained by coupling diazotized o-aminodiphenylethers which are halogenated in the nucleus containing amino-groups with arylides of the general formula IOH ()H firm-W- O H H O X X l CH3 OHa wherein X stands for hydrogen, alkyl or alkoxy, and which products, in a dry state, are dark brown powders, and, when produced on the fiber, dye the same brown tints which are intensive.

21. The azo-dyestuff which corresponds to the formula which product is obtained by coupling the diazotized 4-chloro-2-aminodiphenylether with the arylide from one molecular proportion of benzidine and two molecular proportions of cresctinic acid, which product, when dry, is a brown powder, and, when produced on the fiber, dyes the same brown tints.

22. The azo-dyestuff which corresponds to the formula (|)H OH 0 ll I I 2] O H H C1 CH3 CH3 C1 general formula which product is obtained by coupling the diazowherein R4 stands for the radical of a diazotized o-aminodiphenylether which is halogenated in tized 4 :4 -dichloro-2-aminodiphenylether with the arylide from one molecular proportion of benzidine and two molecular proportions of cresotinic acid, which product, when dry, is a brown powder, and, when produced. on the fiber, dyes the same brown tints.

the arylide from one molecular proportion of tolidine and two molecular proportions of cresctinic acid, which product, when dry, is a brown powder, and when produced on the fiber, dyes 23. The azo-dyestuff which corresponds to the the same brown tints. 5 formula r r r r o H 1 H 0 CH: CH:

GE'RALD BONHOTE.

JACOB DANUSER.

which product is obtained by coupling the diazotized 4 :4-dichloro-2-aminodipheny1ether with 

